Salts of tetranitrodiethylamines



United States Patent SALTS 0F TETRANITRODIETHYLAMINES Karl Klager,Monrovia, Calif.

' No Drawing. Application January 7, 1957 Serial No. 632,945

Claims. (Cl. 260-577) (Granted'under Title 35, US. Code (1952), sec.266) 'The invention described herein maybe manufactured and used by orfor the Government of the United States of America for governmentalpurposes without the payment of any royalties thereon or therefor.

This application is a continuation-in-part of applicants copendingapplication Serial No. 258,976, filed November 29, 1951, now abandoned,for Salts of Tetranitrodiethylamines.

This invention relates to new diethylamines and to a process for thepreparation thereof. Specifically, these new compounds may berepresented by the following structural formula:

in which R1 is ordinarily hydrogen but. may. be a member of the groupincluding .bromine, fluorine, and chlorine. R represents a member of thegroup. including hydrogen, amino, alkyl, varalkyl, and aryl. Thecompounds are usually prepared in the form of salts in which case themember of the group represented by R is replaced by a member of thegroup including sodium or potassium which is associated with one of thetwo nitro groups connected to each terminal carbon .atom. As examples ofdiethylamines coming withinthe scope. of the above formula there may bementioned the following: potassium salts of2,2,2,2-tetranitrodiethylamine,. N-amyl-2,2,2,2'-tetranitrodiethylamine, N buty1-2,2,2',2'-tetranitrodiethylamine, and phenyl-2,2,2,ZGtetranitrodiethylamine;,2,2'-dibromo-2,2,2,2'-tetranitrodiethylamine, and the like.

One object of the invention. isto provide a process for the productionof tetranitrodiethylamines and derivatives thereof. Another-object is toprovide a process for reacting potassium dinitroethanol with. aminesunder moderate, controlled conditions. A further object is to providenew. nitro compounds. 1 Further 0bj6CtS 'Wil1 appear hereinafter.

Prior to the instant invention, investigators in this field found thatalcohols would react with ammonia or amines under drastic conditions toform substituted amines. It has been discovered that potassiumdinitroethanol reacts readily with ammonia or amines in aqueous solutionat moderate temperatures and at atmospheric pressure. The yields arenearly quantitative. Potassium dinitroethanol undergoes reaction withammonia to yield dipotassium 2,2,2',2, tetranitrodiethylamine having thefollowing structure:

IIVOOK H If H NOOK i 77 N0 H NO;

"ice

- where. R represents an alkyl, aryl, or aralkyl group.

Temperatures ranging from 20 to 85 C. may conveniently be employed. Inthe majority of instances, however, it will be found desirableto effectsuch reaction at temperatures of from 50 to 75 C. The compounds producedin this manner may be purified by recrystallization from a suitablesolvent, such as, for example, acetone, methanol, or ethanol.

The dinitroethanol contemplated by the invention is represented, in theform of the potassium salt, by the following formula:

ll TO OK I NC;

., It-will be. evident that the potassium associated with the inwhich Rrepresents either hydrogen, amino, substituted amino, alkyl, aryl, andaralkyl groups. Examples Qf:SllCh compounds are ammonia, hydrazine,substituted hydrazines, amylamine, butylamine, aniline, and the like.

The examples which follow are illustrative of the various types oftetranitrodiethylamines that come within the scope of the invention.They are likewise illustrative of the procedures whereby these newchemical compounds may be synthesized. However, it is to bespecifitially any primary amine of the various types enumerated above,with a nitroethauol of the class described.

Example l.40 gm. potassium dinitroethanol was suspended in a mixture of50 ml. H 0 and 25 m1. ammonia. After heating for two hours. at 6075 C.the mixture was cooled to 0 C. and the precipitated yellow crystals werefiltered off. The yield was. 25 gm. of potassium2,2,2,2'-tetranitrodiethylamine.

Example II.-300 gm. of potassium dinitroethanol was dissolved in 375 ml.H 0 and ml. ammonia at 60 C. and maintained for four hours at 55-60 C.with stirring. After about three hours of stirring a yellow precipitatewas formed. After cooling to 10 C. and filtering, gm. wet dipotassium2,2,2,2-tetranitrodiethylamine was obtained.

Example III.-23.3 gm. potassium 2,2,2',2-tetranitrodiethylamine wassuspended in 120 gm. ice and 80 ml. H 0 and 6 ml. bromine was added at 0C. dropwise with good agitation. The color of the reaction mixturechanged from yellow to brown. The white percipitate was filtered andwashed with water. The yield was 21.8 gm. of 2,2 dibromo-2,2,2',2-tetranitrodiethylamine after crystallization from hexane. The meltingpoint of the white needles was 66-68 C.

Example IV.-40 gm. potassium dinitroethanol was suspended in 66 ml.water and 14.6 amylamine was added at 50 C. to the mixture. After about10 minutes of heating the salt disappeared. The stirring was continuedfor an additional two hours. The mixture was then cooled to roomtemperature and filtered. After washing with ice water, 42 gm. ofdipotassium N-amyl- 3 2,2,2,2tetranitrodiethylamine in the form ofyellow crystals was obtained. The crystals are soluble in methanol,acetone and ethanol.

Example V.40 gm. potassium dinitroethanol and 66 ml. Water were heatedto 55 C. and 13.4 gm. n-butylamine was dropped into the mixture. Afterminutes the salt was completely dissolved. The stirring was continuedfor an additional three hours. After cooling to room temperature, theprecipitate was filtered and washed with water. The yield was 65.5 gm.of dipotassium N-nbutyl-Z,2,2,2-tetranitrodiethylamine in form of yellowcrystals soluble in alcohol and acetone.

Example V1.4O gm. potassium dinitroethanol and 84 ml. water were heatedto 50 C., and 14 gm. aniline was dropped into the suspension. After 10minutes of stirring at 5055 C. a red solution was obtained which wasstirred at the same temperature for an additional two and one-halfhours. After cooling the mixture to room temperature, the crystals werefiltered off and washed with water. Red brown crystals of dipotassiumphenyl- 2,2,2,2-tetranitrodiethylamine were obtained.

The highly nitrated compounds resulting from the above described processare valuable explosives since they have a favorable oxygen balance, arerelatively stable, form uniform crystals, and are smokeless.

The compounds of this invention are useful as high explosives and can beused in any conventional explosive missile, projectile, rocket, or thelike, as the main explosive charge. An example of such a missile isdisclosed in United States Patent No. 2,470,l62, issued May 17, 1949.One way of using the high explosives of this invention in a device suchas that disclosed in United States Patent No. 2,470,162, is to pack thecrystalline explosive in powder form into the warhead of the missile.Alternatively, the crystals can be first pelletized and then packed. Acharge thus prepared is sufficiently insensitive to withstand the shockentailed in the ejection of a shell from a gun barrel or from a rocketlaunching tube under the pressure developed from ignition of apropellant charge, and can be caused to explode on operation of animpact or time fuse-mechanism firing a detonating explosive such as leadazide or mercury fulminate.

Obviously many modifications and variations of the present invention arepossible in the light of the above teachings. It is therefore to beunderstood that within the scope of the appended claims the inventionmay be practiced otherwise than as specifically described.

What is claimed is:

1. Tetranitrodiethylamines having the ionic formula:

5. Dipotassium salts of phenyl-2,2,2,2'-tetranitrodiethylamine.

6. A process for the preparation of tetranitrodiethylamine compounds ofthe class described, which comprises mixing a primary amine having theformula: R NH wherein R represents a member of the group consisting ofhydrogen, phenyl, and the lower alkyls; with potassium dinitroethanol inaqueous suspension at a temperature of between 20 to C., and allowingthe mixture to stand until the reaction between said amine and potassiumdinitroethanol is complete.

7. A process for the preparation of potassium salts oftetranitrodiethylamine compounds which comprises mixing a primary loweralkylamine with potassium dinitroethanol in aqueous suspension at atemperature of between about 20 to 85 C., and allowing the mixture tostand for about two hours.

8. A process for the preparation of dipotassium salts of phenyl-2,2,2',2-tetranitrodiethylamine which comprises suspending potassiumdinitroethanol in water at a temperature of about 60 C. adding theretoaniline, and allowing the mixture to stand until the reaction issubstantially complete.

9. The process which comprises reacting an alkali metal lowerdinitroalcoholate, having at least two nitro groups attached to onecarbon atom and a primary hydroxyl group attached to a second carbonatom adjacent to the aforesaid carbon atom, with a nitrogen compoundcontaining the group NH and selected from the class consisting ofammonia, lower alkyl amines, and hydrazine, and recovering the resultingalkali metal salt of tetranitrodiethylamine.

10. A process for the preparation of dipotassium salts of2,2,2,2-tetranitrodiethylarnine which comprises mixing potassium2,2-dinitroethanol in aqueous suspension with an aqueous solution ofammonia at a temperature between 20 and 85 and allowing the mixture tostand until the reaction between ammonia and potassium dinitroethanol iscomplete, and recovering the dipotassium salts of2,2,2,2-tetranitrodiethylamine.

References Qited in the file of this patent UNITED STATES PATENTS2,731,460 Schenck et al .Tan. 17, 1956

1. TETRANITRODIETHYLAMINES HAVING THE IONIC FORMULA: